Apparatus for the manufacture of high molecular weight polymers



Sept. 4, 1945. A. D. RE'EN APPARATUS FOR THE MANUFACTURE- OF HIGH MOLECULAR WEIGHT POLYMES Filed Sept. 19, 1941 2 Sheets-Sheet l 0 WHSQON RWS." NULS: it 13 III SP 4, 1945 A. D. GREEN 2,384,298

APPARATUS FOR THE MANUFACTURE OF HIGH MOLECULAR WEIGHT POLYMERS Filed Sept. 19, 1941 l2 Sheets-Sheet. 2-

FIG.' -2

Patent-ed Sept. 4, 1945 APPARATUS FOR THE MANUFACTURE OF HIGH MOLECULAR WEIGHT POLYMERS Arthur Donald Green, Cranford, N. J., assignor, by mesne assignments, to Jasco, Incorporated, a corporation of Louisiana yApplication September 19, 1941, SerialNo. 411,440

t s claims. `(ci. 23-260) This invention relates to polymerization processes and apparatus. relates particularly to continuous low temperature polymerization processes; and relates especially to the separation of the solid polymer from the liquid and gaseous reaction mixture components Without loss of gaseous materials.

Isobutylene and many other olens polymerize readily either alone, or with other olens or dioleiins, into very high molecular weight polymer substances in the presence of Friedel Crafts type catalysts at low temperatures, and the polymeric materials are inding many important uses.l To the present, however, the material has usually been prepared by a batch process vin which a reactor vessel is filled with the oleflnic material, which may be isobutylene alone or may be isobutylene mixed with varying proportions of a diolen such as butadiene, isoprene, pentadiene, dimethyl butadiene or other diolens and homologues thereof, or may consist of` other simple olens or `mixtures of the other simple olens with the dioleflns, together with a suitable diluent-refrigerant such as liquid ethylene or a refrigerant such as solid carbon dioxide, with -or without an auxiliary diluent such as ethyl chloride or other low freezing substances. The refrigerant preferably cools the mixture to a temperature below C., and usually below 10 C. 140 C. or to 165 C., and preferably to a temperature ranging between 78 C. and 120 C. or even lower to 165 C.

To the cooled mixture there is then added a suitable Friedel Crafts type catalyst such as a gaseous boron triuoride; or a dissolved active metal halide such as aluminum chloride in solution in a low freezing solvent such as ethyl or methyl chloride, or carbon disulde, or propyl chloride if ultra low temperatures are not desired, or other suitable solvent which will dissolve from about one-half per cent to several per cent ofthe active metalhalide. The polymerization reaction proceeds quickly, -and may reach completion, or the deslredpercentage of completion in a time interval ranging from a fraction of a minute to about ten minutes, depending in part upon the temperature and in part uponv the strength and efficiency of the catalyst used, as well as the purity of the reacting substances.

In the past, when the reaction had reached the desired stage, the reactor was dumped and the desired solidpolymer recovered from. the reaction mixture. This procedure, however, is time consuming and expensive, involving the sudden vaporization of relatively large quantities of inaterial and it entails some loss of unreacted materials and of the remaining diluent-refrigerant or refrigerant, as well as potential danger because of the opportunity for escape of explosive vapors into the atmosphere.

The present invention provides a continuous, recycling, process by which there is a. minimum of loss of unpolymerized and auxiliary materials. Broadly, the invention consists of purification and mixing systems for the reactants and the catalyst, to which is connected a polymerization device, provided with means for the introduction of the'catalyst and for removal of the reaction heat. There is'also provided a polymer recovery member including (if desired) a catalyst quenching means,'a, belt conveyor system for transporting the polymer separated from the excess diluent-refrigerant and means for washing and purfying the recovered polymer, together with a means for removing the solid polymer from the separating chamber with a minimum loss of gaseous materials; and a condensing and purifying system for the Volatile substances as well as separating and other processing means for the polymer.

Thus the invention consists of the process steps, and apparatus members, for mixing the olenic materials and diluent-refrigerant, a reaction chamber, means for preparing the catalyst and discharging it into the reaction chamber, means for removal of the reaction heat, may include means for quenching the polymerization reaction by the addition of a substance which is reactive with the catalyst, such as an alcohol, aldehyde or alkali and includes a separating mechanism hav. ing a closed chamber containing therein a conveyor belt to which the polymerization mixture is delivered, upon which a spray of hot water is discharged to volatilize all of the volatile constituents in the polymerization mixture, leaving behind upon the conveyor belt only the solid polymer, together with an outlet for steam and volatile'hydrocarbons, with a condenser for separating the steamfrom the volatile hydrocarbons as water, a, purification system for the separation of the various volatile hydrocarbons and catalyst if a volatile catalyst is used, and means for removing the solid polymer from the separting chamber with a, minimum of loss of gaseous hydrocarbons together with means for'removing the moisture from the polymer.

Thus an object oi' `the invention is to polymerize an oleflnic mixture at low temperature, and to remove the polymer from the system continuously without loss of unpolymerized components of the reaction while avoiding any danger or industrial hazard from leakage of explosive gases. Other objects and details of the invention will be apparent from the following description when read in connection with' the accom- Y Darwins drawings wherein:

Figure 1 is a diagrammatic view of the apparatus of the invention illustrating the process steps of the invention; and A Figure 2 is a perspective view of the polymer separating member of the invention.

Referring to the gures, there is provided a chamber member I equipped with a plurality of feed lines 2. 3 and 4, of which feed lines 2 and 3 may be used for the delivery tothe mixing chamber. of the various reacting materials such as isobutylene, butadiene, the diluent-refrigerant such as liquid ethylene, if it is used, or a simple diluent such as ethyl or methyl chloride if such' is used. The feed line 4 preferably is used for the delivery of recycled material such as recovered and recycled olenic materials or recovered and recycled diluent-refrigerant, or recovered and recycled diluent. l l

Adjacent to the mixing chamber I is a second mixing system E which is used for the preparation of the catalyst. If boron trifluoride is used for catalyst, this may consist merely of a pressure tank containing liquefied boron trifluoride. If aluminum chloride or analogous solid catalyst is used, the member I may represent a dissolving and purifying system to which' recycled catalyst solvent is delivered through a feed line 8, and fresh catalyst material is delivered through feed line 1. 'Ihe mixing chambers I and 5 are connected, respectively, through transfer lines 8 and 9, to feed measuring pumps II and I2 and further transfer lines ll and I5 to the polymerization reactor Il which is positioned within the cooling chamber I1. The transferrlines may conduct the streams through coolers (not shown). The polymerization reactor I8 preferably consists of a spaced internal coil of tubing.

Within the chamber I1l surrounding the coil I8, there is positioned th'e desired refrigerant. If the refrigerant used is liquid ethylene, the chamber is preferably closed and provided with supply and discharge lines as shown. Of these, the feed line I8 may be used for the supply to the ch'amber I1 of the diluent-refrigerant which may be liquid ethylene, may be liquid propane, or may be other suitable low boiling substances including sulfur dioxide, ammonia and other appropriate refrigerants. When using external cooling, there is normally used a diluent but not a diluent-refrigerant (which acts by vaporizing). A suitable ldischarge line I! is provided for the removal of is preferably connected to a' supply of low freezing liquid suc'h as isopropyl alcohol which serves to convey the heat of reaction from the coil It to th'e solid carbon dioxide. In this instance the line Il serves for discharge of the volatilized carbon dioxide, and the line 2| serves as a drain for the low freezing liquid. 'I'he catalyst transfer line Il is connected to the coil II at several points, one connection being preferably comparatively near tothe entrance end of the tube, conveniently about one-quarter of the length of the tube, suillcient length of tube being allowed to permit of the cooling of the mixed oleflns to substantially the temperature of the refrigerant in the cooling chamber I1.

The polymerization tube I6. is brought out from the chamber I1 and connected to a quench mixer 22 to which a catalyst quenching material such asethyl or isopropyl alcohol is supplied by a transfer line 2l and a pump 2l which draws a supply from a feed line 25. 'The quenched reaction mixture is then delivered through a transfer line 26 into a separatory chamber 21 on to a conveyor belt 28.

The above disclosure shows a coil polymerization system with external cooling, the polymerization occurring within the coil. It is not nec. essary for this invention that such coil type of cooling system be used. Instead, a pot type of reactor may be used with means for the delivery of the reactant and catalyst thereto, means for the cooling of the reactor, reactant supply means, and means for the outflow of the polymerization mixture with the contained soiid polymer. member may take the form of the reactor. shown in the copending application of Sparks and Field, Serial No. 409,909, filed September 6, 1941, or may take the form of the reactor shown in the copending application of Gerlicher, Serial No. 425,- 066, filed December 3l, 1941; and in either event, internal cooling may be utilized with a suillcient quantity of a refrigerant such, as liquid ethylene or liquid methane or solid carbon dioxide to provide the desired low polymerization temperature. The outflow or discharge pipe from any of these alternative reactors may be connected to the pipe I6, as shown in Fig. 1, to deliver the catalyst suspension or slurry to the quenching device 22 and duct 26, and from the duct 26 to the conveyor belt 28.

The conveyor belt 28 may consist of a thin steel l or bronze sheet, or may consist of a wire mesh or a fabric mesh, or 2, proofed fabric mesh covered with a. substance such as synthetic polymer or other material which does not lose too much of its elasticity at relatively low temperature and is not injured by steam or by the materials being vaporized. Adjacent to the top surface of the belt 28 there is provided a steam and hot water spray 29 supplied through a feed line 3|. A discharge Aline 32 is also provided for the removal of volatilized hydrocarbon substances including any diluent-refrigerant which may have been added in the mixing chamber I, and any simple diluent which may have been added; as well as the catalyst solvent. condenser 33 by which vapors from the hot water are condensed and separated in the receiver 35. The volatile hydrocarbon materialsare delivered through a transfer line 36 to a purification system 31 from which they are returned through lines tand 6, respectively, to the oleiln mixing system and catalyst preparing system.

'I'he solid polymer delivered from the transfer line 26 is processed with hot water and Asteam on This.

The line 32 is connected to a The belt 28 passes through a partition 39 in the separatory chamber 21 through a device shown in greater detail in Figure 2. Beyond thepartition 39 there is provided a sealed chamber and an end member 4I to the separating chamber 21. Between the partition 38 and the end member 4I within the sealed chamber, there is provided a pressure of steam or inert gas in excess oi' the pressure within the chamber 21, which is supplied through a feed line 42. This pressure prevents the passage of combustible or toxic vapors through the ypartition 39, and results in the delivery of all of the volatile materials through the line 32 to the purification system.

From the sealed1 chamber the polymer is carried out through the partition 4I on the belt 28 to an exterior roll 43, upon which the solid polymer is disengaged from the conveyor belt 28.

The polymer may then, if desired, be dried by suitable means as shown.

In practicing the invention, the container l is lilled with the desired isooleflnic material or mix'- ture such as isobutylene, together with a suitable diluent-refrigerant, preferably liquid ethylene, the respective materials being delivered through the pipe lines 2, 3 and 4. Simultaneously, the catalyst container 5 is fllled with the desired solution of aluminum chloride or other active halide catalyst, preferably in solution in an alkyl halide such as Iethyl or methyl chloride or in carbon disulfide or other suitable solvent to form a cata.- lyst solution. The oleflnic mixture is delivered by the pump Il to the reaction chamber or polymerization tube i6 within the cooling chamber I1, the tube being immersed in a suitable refrigerant, preferably liquid ethylene, within the cooling chamber I1. i

Simultaneously, the` catalyst solution is delivered through the pipe lines 9 and I5 by the pump I2 to the polymerization coil I6 at` convenient points along its vlength as indicated.

The polymerization occurs in the coil to yield a slurry of solid polymer in the stream of diluentrefrigerant. This slurry is discharged from theA lower end of the polymerization tube i6 into a quenching chamber 22, to which a. supply of ar quenching medium such as methyl, ethyl, propyl or higher alcohol or other oxygenated or alkaline substance is supplied; The alcohol or other quenching substance reacts with the aluminum chloride in the solution to destroy its catalytic power.

This quenching apparently is accomplished by a metathetical reaction which converts the aluminum chloride' into an oxygenated or other compound, perhaps a double compound with the alcohol, which is of such low catalytic power, or so wholly lacking in catalytic power, as to prevent the further catalysis of residual polymeric substances during the warming-up operation.'

The slurry is then discharged through the pipe line 26 on to the belt 28, where it is washed and brought up nearly to the temperature of boiling water by a spray of hot water and steam delivered from the pipes 29 and 3|. The temperature of boiling water or near to this temperature is sum- -ciently high to volatilize all of the diluent-refrigerant, all of the residual olefinic mixture and all of the catalyst solvent, as well as some of the alcohol if the lower alcohols are used. The re'-v sidual catalyst and water fall to the-bottom of the chamber 21 and are drained away through the drain pipe 38. The polymer is carried between rolls in the partition while o n the belt 28 into the sealed chamber 40 within which there is portion is drained by wayof the pipe line shown' and the gaseous or organic liquid portions are led through the pipe line $6 to the puriicatlon system 31 for recycling, if desired. Simultaneously, the polymer is passed outward from the sealed chamber 40 through the rolls in the secy ond partition 4I, removed from the belt 2l at the roll 43 and the excess moisture removed by appropriate means.

The system above described is particularly advantageous for polymerization reactions in which a partial polymerization only occurs, leaving a substantial quantity of reactants, diluent-refrigerant and catalyst solvent to be removed from the solid polymer, since the system is particularly convenient for the necessary recycling operations.

Alternatively,'especially when the polymeriza- 'tion reaction is producing simple polyisobutylene,

relatively small amounts only of material remain unpolymerized, especially if solid carbon dioxide is used as the refrigerant, and under these circumstances, recycling is not necessary. The above system-is, however, particularly advantageous because of the reduction of industrial and lire hazard by avoiding the discharge of any combustible or poisonous carbonaceous materials into the atmosphere of the workroom.

The above disclosure presents a tube reactor, in which most of the cooling is obtained by a cooling jacket around the reaction chamber. The system of the invention is equallyl applicable to an overflow reactor in which a mixture of diluent-refrigerant and olefin material is continuously delivered to a reaction chamber such as a reaction kettle, with or Without a cooling jacket for refrigerant; and a catalyst is added either to the feed stream or to the rapidly stirred kettle contents, and a continuous output stream of polymer slurry withdrawn to the quenching device and sealed chamber, as shown in the above disclosure. Batch type reactor kettles are readily f modified for continuous service by providing an overflow outlet from which the overiiow stream is taken to the quenching means and separatory chamber. As the reactor means, it is satisfactory to use a simple jacketed kettle with a stirrer; or

a belt conveyor upon which the polymerization reaction occurs may be utilized, or a cardoid type of reaction kettle with power stirring mechanism may also .be used.

It should be noted that the device of the invention asyabove disclosed is particularly advantageous for the making of either solid, semi-solid or liquid polymers. If solid polymers are made, they are present as a slurry in a relatively nonviscous liquid and are readily handled in the device of the invention. In making liquid polymers, they mix with or dissolve in the diluent-refrigerant. if such is used, or remain liquid in the coil if a diluent or diluent-refrigerant is not used, and accordingly are equally readily ha'ndled.

Thus the practice of the invention provides a recycle system in which the oleiinic materials are mixed, chilled to low temperature, mixed` in a polymerization coil with catalyst solution, passed rapidly through the polymerization coil at low A gaseous oleiinic material, catalyst solvent and quenching material are separated and purified for the preparation of further portions of polymerization mixture and catalyst solvent.

While there is above disclosed lbut a single embodiment of the device of the invention, it is possible to produce still other embodiments without departure from the inventive concept herein disclosed and it is therefore desired that the existence and utility of such other embodiments be recognized both with respect to the above specification and the subjoined claims.

The invention claimed is: Y

1. An improved apparatus for recovery of solid constituents from a reaction mixture composed of solid and liquid vaporizable constituents which comprises a separatory chamber, an auxiliary chamber directly adjacent said separatory chamber, an opening in the partition wall between the separatory chamber and the auxiliary chamber, an opening in an outer wall of said auxiliary chamber, conveyor means extending thru said openings. means for Asupplying a continuous stream of said reaction mixture to said conveyor, means forintroducing a iiuid heating medium into said separatory chamber, a vapor line connected to said separatory chamber for withdrawing volatilized constituents from said-chamber, roller members adjacent said openings and pressing against said conveyor means, and conduit means connected to a source of gas under pressure communicating with said auxiliary chamber.

2. An improved apparatus for the recovery of solid olefinic polymers from a. low-temperature, oleflnic reaction mixture composed of portions of solid polymer and portions of vaporizable liquid. refrigerant and reactant materials comprising in .combination a reactor vessel, a transfer line from said reactor for the discharge of reaction material, a separatory chamber connected to said transfer line, an auxiliary chamber adjacent to said separatory chamber and having a common partition wall therebetween, an opening in the said partition wall between the said separatory chamber and the said auxiliary' chamber, an opening in an outer wall of said auxiliary chamber, a pulley within said separatory chamber, adjacent the connection to said transfer line, al pulley outside of the opening in the outer wall of said auxiliary chamber, a conveyor belt passing over said pulleys and through the said openingsin the walls of said separatory chamber and said auxiliary chamber, a nozzle cooperating between said transfer line and said conveyor belt for delivering a stream of the polymer-liquid material from said reactor to said conveyor belt,

a spray nozzle member within said separatory chamber, a supply of steam to said spray nozzle member cooperating with said conveyor belt, an outlet pipe connected to said separatory chamber for the removal therefrom of gaseous material, a drain from the bottom of said separatory chamber for the removal of liquid therefrom, roller members cooperating in said openings with said conveyor belt for closing said openings, and a pipe line connected to said auxiliary chamber for the delivery of gas under pressure thereto.

3. An improved apparatus for the recovery of solid olenic polymers from a low-temperature, oleilnic reaction mixture composed of portions of solid polymer and portions of vaporizable liquid refrigerant and reactant materials comprising in combination a reactor vessel, a transfer line from said reactor for the discharge of reaction material, a pipe connection to said transfer line for the admixture of a quenching agent thereinto, a separatory chamber connected to said transfer line, an auxiliary chamber adjacent to said sep-v aratory chamber and having a common partition wall therebetween, an opening in the said partition wall between the said separatory chamber and the said auxiliary chamber, an opening in an outer wall of said auxiliary chamber, a pulley within said separatory chamber, adjacent the connection to said transfer line, a pulley outside of the opening in the outer wall of said auxiliary chamber, a conveyor belt passing over said pulleys and through the said openings in the walls of said separatory chamber and said auxiliary chamber, a nozzle cooperating between said transfer line and said conveyor beltl for deliver-v ing a stream of the polymer-liquid material from said reactor to said conveyor belt, a spray nozzle member within said separatory chamber, a supply of steam of said spray nozzle member cooperating with said conveyor belt, an outlet pipe connected to said separatory chamber for the removal therefrom of gaseous material, a drain from the bottom of said separatory chamber for the removal of liquid therefrom, roller members cooperating in said openings with said conveyor belt for closing said openings, and a pipe line connected to said auxiliary chamber for the de7 livery of gas under pressure thereto.

4. An improved apparatus for the recovery of solid olefinic polymer components from a reaction mixture composed of solid polymer portions and liquid vaporizable portions comprising a chamber having a partition therein dividing it into a separatory chamber and an auxiliary chamber, a pair of pulleys, one within said chamber, one outside of said chamber, openings in said partition and an end of said chamber, aligned between said pulleys, a conveyor belt passing over said pulleys, roller members within said openings cooperating with said conveyor belt substantially to close said l'openings against the passage of gas while allowing movement of said conveyor belt and solid material therein, a spray nozzle cooperating with said conveyor belt for the delivery of steam and -water to solid material thereon, a low-temperature polymerization reactor and a transfer line connecting said reactor to the said separatory chamber, a delivery nozzle within said separatory chamber connected to said transfer line for the delivery of mixture of solid polymer and liquid material to said conveyor belt, a discharge pipe from said separatory chamber for the removal of volatilized material, and a gas inlet to said auxiliary chamber for the production therein of a gas plenum to prevent the passage of volatilized components outward from said separatory chamber.

5. A separator comprising a chamber, a partition therein, a pair of pulleys, one within said chamber, another outside of said chamber, openings ln said chamber wall and said partition aligned with said pulleys, a conveyor belt passing over said pulleys through said openings, rollers in said openings for substantially closing said openings against the passage of gas, a nomic for delivery of mixed solid and liquid material to said through which said conveyor belt also passes,

seal rollers in said openings cooperating with said belt to limit the passage of gas therealong, a supply oi' gas under pressure connected to the space in said casing between said partition, and the end of said casing through which Vsaid conveyor belt passes, a spray head for the delivery of washf ing material onto said conveyor belt and a discharge/nozzle vcooperating with said conveyor beltI l0 for the delivery thereunto of a mixture of solid polymer and volatilizable refrigerant.

ARTHUR DONALD GREEN. 

